WO2011009704A1 - Fibres faites de copolymères de propylène et 1-pentène - Google Patents

Fibres faites de copolymères de propylène et 1-pentène Download PDF

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Publication number
WO2011009704A1
WO2011009704A1 PCT/EP2010/059472 EP2010059472W WO2011009704A1 WO 2011009704 A1 WO2011009704 A1 WO 2011009704A1 EP 2010059472 W EP2010059472 W EP 2010059472W WO 2011009704 A1 WO2011009704 A1 WO 2011009704A1
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WO
WIPO (PCT)
Prior art keywords
pentene
propylene
copolymers
copolymer
fibres
Prior art date
Application number
PCT/EP2010/059472
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English (en)
Inventor
Monica Galvan
Claudio Cavalieri
Antonio Passerini
Gabriella Sartori
Original Assignee
Basell Poliolefine Italia S.R.L.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Basell Poliolefine Italia S.R.L. filed Critical Basell Poliolefine Italia S.R.L.
Publication of WO2011009704A1 publication Critical patent/WO2011009704A1/fr

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Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/30—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising olefins as the major constituent
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/005—Synthetic yarns or filaments
    • D04H3/007—Addition polymers

Definitions

  • the present invention relates to filaments and fibers made from random copolymers of propylene with 1-pentene.
  • fibres are also included the manufactured products similar to fibres, such as fibrils and cut filaments (staple fibres).
  • the fibres can be advantageously used for the production of soft non-woven fabrics.
  • propylene homopolymers have excellent spinnability, but since their melting point is relatively high, i.e. typically up to 165°C, they require high temperatures for producing non-woven fabrics by thermal processes, like thermal spunbonding. Moreover, fibers and non-woven fabrics obtained from propylene homopolymers have rather poor hand. The hand or feel of a fabric plays an important role since there is a growing demand on the market for "soft hand" no n- woven fabrics. Propylene copolymers can be conveniently used to overcome the drawbacks of propylene homopolymers.
  • WO 99/01485 relates to a process for producing a propylene 1-pentene polymer in the presence of a Ziegler-Natta catalyst system with the monomers reactants being in the vapor phase.
  • WO 96/24623 relates to a copolymer of propylene and pentene, together with a process for producing such copolymer and a polymer composition.
  • the only use taught by this application are films prepared in the examples.
  • fibres made from copolymers of propylene with 1-pentene exhibit a high tenacity value and yet maintain a good elongation at break value, furthermore they have excellent values of softness.
  • An object of the present invention is a fibre comprising a copolymers of propylene and 1-pentene containing from 0.1% to 20% by weight of 1-pentene derived units; preferably the content of 1- pentene derived units ranges from 0.5 % to 10% by weight more preferably from 1% to 5% by weight, even more preferably from 1.2 to 3% by weight.
  • the copolymer of the present invention are further endowed of a value of melt flow rate (MFR) ranging from 0.1 to 100 g/10 min, preferably the MFR ranges from 1 to 50 g/10 min, more preferably the MFR ranges from 5 to 30 g/10 min.
  • MFR melt flow rate
  • the propylene/ 1-pentene copolymer of the fibre of the present invention is further endowed with: - a melting point measured by using DSC ranging from 135 to 160° C; and
  • solubility in xylene at room temperature below 10 wt%, preferably below 5 wt%, more preferably below 3 wt%.
  • the fibre according to the present invention typically exhibits a value of tenacity higher than 18 cN/tex; preferably higher than 20 cN/tex and a value of elongation at break higher than 190%, preferably higher than 200%.
  • Futhermore the fibre according to the present invention typically exhibits a value of softness higher than 870 1/gr, preferably higher than 900 1/gr.
  • the fibres according to the present invention have a titre ranging from 1 to 8 dtex, preferably 1.5 to 4 dtex, more preferably from 2 to 3 dtex.
  • the fibers of the present invention can contain formulations of stabilizers suited for obtaining a skin-core structure (skin-core stabilization), or a highly stabilizing formulation. In the latter case, a superior resistance to aging is achieved for durable nonwovens.
  • the copolymers of propylene and 1-pentene can be directly prepared in at least one polymerization step in presence of highly stereospecific heterogeneous
  • the copolymers of propylene and 1-pentene can be prepared by subjecting to chemical degradation a precursor copolymer of propylene and 1-pentene having MFR(Al).
  • the copolymers of propylene and 1-pentene are obtainable by a process comprising the following steps:
  • the copolymer of the present invention can be prepared by polymerisation in the presence of Ziegler-Natta catalysts.
  • An essential component of said catalysts is a solid catalyst component comprising a titanium compound having at least one titanium-halogen bond, and an electron- donor compound, both supported on a magnesium halide in active form.
  • Another essential component (co-catalyst) is an organoaluminium compound, such as an aluminium alkyl compound.
  • An external donor is optionally added.
  • the catalysts generally used in the process of the invention are capable of producing polypropylene with a value of xylene insolubility at room temperature greater than 90%, preferably greater than 95%.
  • the solid catalyst components used in said catalysts comprise, as electron-donors (internal donors), compounds selected from the group consisting of ethers, ketones, lactones, compounds containing N, P and/or S atoms and and esters of mono- and dicarboxylic acids.
  • electron-donors internal donors
  • Particularly suitable electron-donor compounds are 1,3- diethers of formula:
  • R and R are the same or different and are C 1 -C 18 alkyl, C 3 -C 18 cycloalkyl or C 7 -C 18 aryl radicals; R and R are the same or different and are C 1 -C 4 alkyl radicals; or are the 1,3-diethers in which the carbon atom in position 2 belongs to a cyclic or polycyclic structure made up of 5,6, or 7 carbon atoms, or of 5-n or 6-n' carbon atoms, and respectively n nitrogen atoms and n' heteroatoms selected from the group consisting of N, 0 , S and Si, where n is 1 or 2 and n' is 1, 2, or 3, said structure containing two or three unsaturations (cyclopolyenic structure), and optionally being condensed with other cyclic structures, or substituted with one or more substituents selected from the group consisting of linear or branched alkyl radicals; cycloalkyl, aryl, aralkyl, alkaryl radicals and
  • dieters are 2-methyl-2-isopropyl-l,3-dimethoxypropane, 2,2- diisobutyl- 1,3-dimethoxypropane, 2-isopropyl-2-cyclopentyl- 1 ,3-dimethoxypropane, 2- isopropyl-2-isoamyl- 1,3-dimethoxypropane, 9,9-bis (methoxyrnethyl)fluorene.
  • Suitable electron-donor compounds are phthalic acid esters, such as diisobutyl, dioctyl, diphenyl and benzylbutyl phthalate.
  • the preparation of the above mentioned catalyst components is carried out according to various methods. For example, a MgC12.nROH adduct (in particular in the form of spheroidal particles) wherein n is generally from 1 to 3 and ROH is ethanol, butanol or isobutanol, is reacted with an excess of TiCU containing the electron-donor compound. The reaction temperature is generally from 80 to 120' C. The solid is then isolated and reacted once more with TiCU, in the presence or absence of the electron-donor compound, after which it is separated and washed with aliquots of a hydrocarbon until all chlorine ions have disappeared.
  • the titanium compound expressed as Ti, is generally present in an amount from 0.5 to 10% by weight.
  • the quantity of electron-donor compound which remains fixed on the solid catalyst component generally is 5 to 20% by moles with respect to the magnesium dihalide.
  • the titanium compounds which can be used for the preparation of the solid catalyst component, are the halides and the halogen alcoholates of titanium. Titanium tetrachloride is the preferred compound.
  • the Al-alkyl compounds used as co-catalysts comprise the Al-trialkyls, such as Altriethyl, Al- triisobutyl, Al-tri-n-butyl, and linear or cyclic Al-alkyl compounds containing two or more Al atoms bonded to each other by way of O or N atoms, or SO 4 or SO 3 groups.
  • Al-trialkyls such as Altriethyl, Al- triisobutyl, Al-tri-n-butyl, and linear or cyclic Al-alkyl compounds containing two or more Al atoms bonded to each other by way of O or N atoms, or SO 4 or SO 3 groups.
  • the Al-alkyl compound is generally used in such a quantity that the Al/Ti ratio be from 1 to
  • the electron-donor compounds that can be used as external donors include aromatic acid esters such as alkyl benzoates, and in particular silicon compounds containing at least one Si-OR bond, where R is a hydrocarbon radical.
  • silicon compounds are (tert-butyl)2Si(OCH3)2, (cyclohexyl)(methyl)Si(OCH3)2, (cyclopentyl) 2 Si(OCH 3 ) 2 , (phenyl) 2 Si(OCH 3 ) 2 and (l,l,2-trimethylpropyl)Si(OCH 3 )3, which is preferred.
  • 1,3-diethers having the formulae described above can also be used advantageously. If the internal donor is one of these dieters, the external donors can be omitted. In particular, even if many other combinations of the previously said catalyst components may allow to obtain propylene polymer compositions according to the present invention, the copolymers are preferably prepared by using catalysts containing a phthalate a inside donor and (cyclopentyl)2Si(OCH 3 )2 as outside donor, or the said 1 ,3-di ethers as inside donors.
  • copolymers according to the present invention are produced in accordance with known polymerisation processes.
  • a polymerisation process is carried out in one or more stage(s).
  • the copolymers are prepared in sequential stages. In each stage the operation takes place in the presence of the copolymer obtained and the catalyst in the preceding stage.
  • the copolymers are produced by a polymerisation process carried out in at least two interconnected polymerisation zones.
  • the process according to the preferred process is illustrated in EP application 782 587.
  • the said process comprises feeding the monomers to said polymerisation zones in the presence of catalyst under reaction conditions and collecting the polymer product from the said polymerisation zones.
  • the growing polymer particles flow upward through one (first) of the said polymerisation zones (riser) under fast fiuidisation conditions, leave the said riser and enter another (second) polymerisation zone (downcomer) through which they flow downward in a densified form under the action of gravity, leave the said downcomer and are reintroduced into the riser, thus establishing a circulation of polymer between the riser and the downcomer.
  • the velocity of transport gas into the riser is higher than the transport velocity under the operating conditions, preferably from 2 to 1 5 m/s.
  • the copolymers and the gaseous mixture leaving the riser are conveyed to a solid/gas separation zone.
  • the solid/gas separation can be effected by using conventional separation means.
  • the copolymers enter the downcomer.
  • the gaseous mixture leaving the separation zone is compressed, cooled and transferred, if appropriate with the addition of make-up monomers and/or molecular weight regulators, to the riser.
  • the transfer can be effected by means of a recycle line for the gaseous mixture.
  • the control of the copolymer circulating between the two polymerisation zones can be effected by metering the amount of polymer leaving the downcomer using means suitable for controlling the flow of solids, such as mechanical valves.
  • the operating parameters are those that are usual in gas-phase olefin polymerisation process, for example between 5O 0 C to 120 0 C.
  • This first stage process can be carried out under operating pressures of between 0.5 and 10 MPa, preferably between 1.5 to 6 MPa.
  • one or more inert gases are maintained in the polymerisation zones, in such quantities that the sum of the partial pressure of the inert gases is preferably between 5% and 80% of the total pressure of the gases.
  • the inert gas can be nitrogen or propane, for example.
  • the various catalysts are fed up to the riser at any point of the said riser. However, they can also be fed at any point of the downcomer.
  • the catalyst can be in any physical state, therefore catalysts in either solid or liquid state can be used.
  • the copolymers and polymer compositions may be blended with additives commonly employed in the art, such as nucleating agents, colorants and fillers in addition to the abovementioned stabilisers.
  • the fibres of the present invention can be prepared by way of any known melt spin process.
  • the chemical degradation step (2) can be carried out by treating the precursor copolymer of propylene and 1 - pentene or copolymer of propylene and 1-pentene precursor with appropriate amounts, preferably from 0.001 to 0.20 wt%, more preferably from 0.04 to 0.10 wt%, of free radical initiators according to processes well-known in the art.
  • the chemical degradation is carried out by contacting under high shear conditions the polymeric material with at least one free radical initiator at a temperature equal to or higher that the decomposition temperature of the free radical initiator.
  • Preferred free radical initiators are peroxides having a decomposition temperature ranging from 150° to 250 0 C, such as di-tert-butyl peroxide, dicumyl peroxide, the 2,5-dimethyl- 2,5-di (tert-butylperoxy)hexyne, and 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane (traded by Akzo under the name Luperox 101 or Trigonox 101).
  • Fibers or filaments comprising copolymer of propylene and 1-pentene of the invention may be prepared using processes and apparatuses well known in the art, i.e. by melt-spinning the propylene copolymer in conventional devices suitable for producing single or composite fibers or filaments.
  • the composite fibers or filaments may have a "sheath-core structure".
  • fibers or filaments having a sheath-core structure is meant herein fibers or filaments having an axially extending interface and comprising at least two components, i.e. at least an inner core and at least an outer sheath, said at least two components comprising different polymeric materials and being joined along the axially extending interface.
  • sheath thickness may be uniform or the sheath thickness may not be uniform around the circumference of a fiber or filament cross-section.
  • Said fibers or filaments having sheath-core structure can be produced using conventional melt-spin equipments having concentric annular dies.
  • the copolymer of propylene and 1-pentene of the invention may be conveniently used to for the outer sheath of fibers or filaments having a sheath-core structure.
  • the inner core may comprise any polymeric material commonly used for spunbonding applications, depending on the desired end properties of the composite fibers or filaments.
  • the sheath-core fibers or filaments comprise 50-90 wt%, more preferably 65-80 wt%, of polymeric material forming the core-layer and 10-50 wt%, more preferably 20-35 wt%, of the copolymer of propylene and 1-pentene of the invention forming the outer sheath-layer.
  • sheath-core fibers or filaments comprising 70 wt% of polymeric- material forming the core layer and 30 wt% of the copolymer of propylene and 1-pentene of the invention forming the outer sheath.
  • Fibers or filaments having improved tenacity/softness balance in combination with excellent spinnability can be conveniently prepared using the copolymer of propylene and 1-pentene of the invention, said fibers or filaments having sheath-core structure, wherein the skin layer comprises the propylene polymer composition of the invention and core layer comprises a propylene homopolymer having low xylene-soluble fraction at 25°C, preferably lower than 5.0 wt%, more preferably lower than 3 wt%, and high flexural modulus, preferably higher than 1100 MPa, more preferably higher than 1300 MPa.
  • Said propylene homopolymers are commercially available.
  • the skin layer of fibers or filaments of the invention having sheath-core structure represent a proportion ranging from 20 to 40 wt% with respect to the whole weight of the filament.
  • IV Intrinsic viscosity
  • the Softness Index of fibers is determined.
  • the Softness Index is calculated as weight (1/g) of a bundle of fibers, whose length is determined in standard conditions.
  • a fiber bundle of about 4000 dtex in linear density and 0.6 m in length is prepared.
  • the end of the bundle is fixed on the clamps of the twist measuring device (Torcimetro Negri e Bossi SpA) and a 120 leftward twist runs applied.
  • the twisted bundle is taken off from the device carefully avoiding any un-twisting.
  • the two ends of the twisted bundle are joint and the halves are wound around each other until the bundle looks like a rope. 3 specimens are prepared for each test.
  • the bundle is bent in two and the ends are fixed between the rolls of a Clark softness tester keeping a distance of 1 cm between the two halves.
  • the device is rotated rightwards and stopped when the bundle reverses its bending direction, taking note of the rotation angle (a). Then, the bundle is rotated leftward and till it reverses its bending side, taking note of the rotation angle (b).
  • Each of the two angles, a and b should not exceed the limits of 45°+- 15°.
  • the bundle is removed from the device and cut to a height (h) corresponding to that previously measured.
  • the cut bundle is weighted by an analytical balance with a precision of 0.1 mg.
  • the Softness index is calculated from the formula:
  • the test is based on ASTM method D- 1774-64. The method concerns procedures for the measurements of the elastic behaviour of fibres by assessing their ability to recover strain or their original dimension following a known extension.
  • the multifilament sample subjected to the test is 40 cm length and has a titre of 500 dtex. The operative conditions are reported in the following table A.
  • the maximum spinning speed gives indication of the spinnability of the propylene polymer composition of the invention.
  • the value corresponds to the highest spinning rate that can be maintained for 30 minutes with no filament break.
  • the solid catalyst component is used with dicyclopentyldimethoxysilane (DCPMS) as external-donor component and triethylaluminium.
  • DCPMS dicyclopentyldimethoxysilane
  • Copolymers are prepared by polymerising propylene and 1 -pentene in the presence of the above catalyst under continuous conditions in a plant comprising a gas-phase polymerisation apparatus.
  • the apparatus comprises two interconnected cylindrical reactors (riser and downcomer). Fast fluidisation conditions are established in the riser by recycling gas from the gas-solid separator.
  • the polymer composition shows a narrow distribution of the molecular weights obtained without using a liquid barrier, the hydrogen concentration is kept at the same concentration in both riser and downcomer and the hexene- 1 is fed only into the downcomer.
  • the polymer particles exiting the reactor are subjected to a steam treatment to remove the reactive monomers and volatile substances and then dried.
  • Propylene and 1 -hexene have been polymerized by using the same procedure indicated in example 1 of WO 2005/059210 to obtain a polymer having an MFR of 2.
  • the polymer obtained has the characteristics indicated in table 2.
  • the obtained copolymer has been spun to produce fibres. The spinning conditions and the proprieties of the fibres thus obtained are reported in
  • Propylene and 1-butene have been polymerized by using the same procedure described in example 1 but using 1-butene instead of 1 -pentene.
  • the polymer obtained has the characteristics indicated in table 2.
  • the obtained copolymer has been spun to produce fibres. The spinning conditions and the proprieties of the fibres thus obtained are reported in Table 3.
  • the copolymer of example 1 and comparative examples 1 and 2 are stabilised by adding a stabiliser package suitable for fibres and a visbroking agent luperox 101®.
  • the visbreaked pellets obtained are spun to produce fibres.
  • the spinnability tests are carried out at 280 0 C and spinning speed in thermal bonding standard conditions.
  • the draw ratio is 1.5.
  • the spinning conditions and the proprieties of the fibres thus obtained are reported in Table 3.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Artificial Filaments (AREA)

Abstract

La présente invention concerne une fibre de thermoliage. Ladite fibre comprend des copolymères de propylène et 1-pentène, la quantité d’unités dérivées de 1-pentène étant de 0,1 % à 20 % en poids. Lesdits copolymères possédant une valeur d’indice de fluidité (MFR) variant de 0,1 à 100 g/10 min.
PCT/EP2010/059472 2009-07-21 2010-07-02 Fibres faites de copolymères de propylène et 1-pentène WO2011009704A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP09165965 2009-07-21
EP09165965.6 2009-07-21
US27315809P 2009-07-31 2009-07-31
US61/273,158 2009-07-31

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WO2011009704A1 true WO2011009704A1 (fr) 2011-01-27

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013004803A1 (fr) * 2011-07-06 2013-01-10 Basell Poliolefine Italia S.R.L. Copolymère statistique du propylène comportant du 1-hexène

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US2388225A (en) * 1941-03-15 1945-10-30 Du Pont Process for polymerizing olefinic materials
EP0045977A2 (fr) 1980-08-13 1982-02-17 Montedison S.p.A. Composants et catalyseurs pour la polymérisation d'oléfines
US4399054A (en) 1978-08-22 1983-08-16 Montedison S.P.A. Catalyst components and catalysts for the polymerization of alpha-olefins
US4472524A (en) 1982-02-12 1984-09-18 Montedison S.P.A. Components and catalysts for the polymerization of olefins
EP0361493A1 (fr) 1988-09-30 1990-04-04 Himont Incorporated Diéthers utilisables dans la préparation des catalyseurs Ziegler-Natta et leur préparation
US5478646A (en) * 1989-08-25 1995-12-26 Mitsui Toatsu Chemicals, Inc. Polypropylene fiber and a preparation process thereof
WO1996024623A1 (fr) 1995-02-09 1996-08-15 Sastech (Proprietary) Limited Copolymeres propylene-pentene-1, procede pour les preparer et compositions les contenant
EP0728769A1 (fr) 1995-02-21 1996-08-28 Montell North America Inc. Composants et catalyseurs pour la polymérisation d'oléfines
EP0782587A1 (fr) 1995-07-20 1997-07-09 Montell Technology Company bv Procede et appareil de polymerisation en phase gazeuse d'alpha-olefines
WO1999001485A1 (fr) 1997-07-04 1999-01-14 Sasol Technology (Proprietary) Limited Procede de polymerisation en phase gazeuse permettant de produire des copolymeres de propylene/1-pentene
WO1999019547A1 (fr) * 1997-10-10 1999-04-22 Exxon Chemical Patents Inc. Polypropylene pour fibres et tissus
JP2002115118A (ja) * 2000-10-11 2002-04-19 Daiwabo Co Ltd 繊維およびその繊維組成物
WO2002052076A1 (fr) * 2000-12-21 2002-07-04 3M Innovative Properties Company Microfibres chargees, articles microfibrilles et leur utilisation
US6476172B1 (en) * 2001-07-27 2002-11-05 Fina Technology, Inc. Metallocene catalyzed propylene-α-olefin random copolymer melt spun fibers
WO2005059210A1 (fr) 2003-12-19 2005-06-30 Basell Poliolefine Italia S.R.L. Fibres fabriquees a partir de copolymeres de propylene et d'hexene-1
US20060008643A1 (en) * 2002-08-12 2006-01-12 Lin Chon Y Polypropylene based fibers and nonwovens

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2388225A (en) * 1941-03-15 1945-10-30 Du Pont Process for polymerizing olefinic materials
US4399054A (en) 1978-08-22 1983-08-16 Montedison S.P.A. Catalyst components and catalysts for the polymerization of alpha-olefins
EP0045977A2 (fr) 1980-08-13 1982-02-17 Montedison S.p.A. Composants et catalyseurs pour la polymérisation d'oléfines
US4472524A (en) 1982-02-12 1984-09-18 Montedison S.P.A. Components and catalysts for the polymerization of olefins
EP0361493A1 (fr) 1988-09-30 1990-04-04 Himont Incorporated Diéthers utilisables dans la préparation des catalyseurs Ziegler-Natta et leur préparation
US5478646A (en) * 1989-08-25 1995-12-26 Mitsui Toatsu Chemicals, Inc. Polypropylene fiber and a preparation process thereof
WO1996024623A1 (fr) 1995-02-09 1996-08-15 Sastech (Proprietary) Limited Copolymeres propylene-pentene-1, procede pour les preparer et compositions les contenant
EP0728769A1 (fr) 1995-02-21 1996-08-28 Montell North America Inc. Composants et catalyseurs pour la polymérisation d'oléfines
EP0782587A1 (fr) 1995-07-20 1997-07-09 Montell Technology Company bv Procede et appareil de polymerisation en phase gazeuse d'alpha-olefines
WO1999001485A1 (fr) 1997-07-04 1999-01-14 Sasol Technology (Proprietary) Limited Procede de polymerisation en phase gazeuse permettant de produire des copolymeres de propylene/1-pentene
WO1999019547A1 (fr) * 1997-10-10 1999-04-22 Exxon Chemical Patents Inc. Polypropylene pour fibres et tissus
JP2002115118A (ja) * 2000-10-11 2002-04-19 Daiwabo Co Ltd 繊維およびその繊維組成物
WO2002052076A1 (fr) * 2000-12-21 2002-07-04 3M Innovative Properties Company Microfibres chargees, articles microfibrilles et leur utilisation
US6476172B1 (en) * 2001-07-27 2002-11-05 Fina Technology, Inc. Metallocene catalyzed propylene-α-olefin random copolymer melt spun fibers
US20060008643A1 (en) * 2002-08-12 2006-01-12 Lin Chon Y Polypropylene based fibers and nonwovens
WO2005059210A1 (fr) 2003-12-19 2005-06-30 Basell Poliolefine Italia S.R.L. Fibres fabriquees a partir de copolymeres de propylene et d'hexene-1

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013004803A1 (fr) * 2011-07-06 2013-01-10 Basell Poliolefine Italia S.R.L. Copolymère statistique du propylène comportant du 1-hexène
CN103649137A (zh) * 2011-07-06 2014-03-19 巴塞尔聚烯烃意大利有限责任公司 丙烯与1-己烯的无规共聚物
US9527935B2 (en) 2011-07-06 2016-12-27 Basell Poliolefine Italia S.R.L. Random copolymer of propylene with 1-hexene

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